Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals

Definitions

• One process for the preparation of glycidyl esters is based on a reaction of the sodium or potassium salt of acrylic or methacrylic acid with epichlorohydrin (U.S. Pat. Nos. 2,556,075 and 2,537,981), optionally with the addition of catalytic amounts of tetramethylammonium chloride.
• the charge may further contain auxiliary agents such as stabilizers, for example, hydroquinone monomethyl ether, hydroquinone, phenothiazine, or N,N'-diphenyl-para-phenylenediamine.
• auxiliary agents such as stabilizers, for example, hydroquinone monomethyl ether, hydroquinone, phenothiazine, or N,N'-diphenyl-para-phenylenediamine.
• the process may be carried out in the following manner, for example:
• the alcohol distillate (methyl methacrylate in azeotropic mixture with methanol) starts to pass over at an overhead temperature of about 30° to 36° C. As soon as no further alcohol distillate is observed, excess methyl methacrylate is drawn off at an increased overhead temperature (about 50° C.).
• the residual crude ester can be substantially degassed, that is to say, freed of methyl methacrylate. The degassed crude ester can then be vacuum distilled. A pure product is obtained in a very good yield.
• a mixture of 70.0 kg (945 moles) of glycidol, 280 kg (2800 moles) of methyl methacrylate, 120 ppm of 1,4-diazabicyclo(2,2,2)octane, 30 ppm of KOH (in methanol), and 200 ppm of N,N'-diphenyl-para-phenylenediamine (as a stabilizer) is charged into a 500-liter V4A agitated vessel having a 4-meter steel column packed with porcelain Raschig rings and equipped with water and brine reflux condenser, interchangeable receiver, reflux control, and vacuum control. A vacuum is produced and the vessel is heated by means of circulating hot water. At a vessel temperature of 60° C.
• a distillate starts passing over from the alcoholysis with a reflux ratio of 2:1.
• the vessel temperature rises to 70° C., and the overhead temperature is held between 33° and 36° C. by adjustment of the reflux ratio of 5:1.
• unreacted methyl methacrylate is withdrawn at a reflux ratio of 1:1 and a temperature of 50° C.
• the crude glycidyl methacrylate ester formed can be degassed down to a residual gas content of about 10%. After further degassing at 110° C.
• the ester formed in the vapor space and a vacuum of 30 mm Hg, can be distilled at 115° C. in the vapor space and 1 to 2 mm Hg. Yields over 80% are observed.
• the total time usually ranges from about 6 to 9 hours.
• a mixture of 475 g (6,41 moles) of glycidol, 2000 g (20 Mol) of methyl methacrylate 200 ppm of 1,4-diazabicyclo(2,2,2)octane and 200 ppm of N,N'-diphenyl-p-phenylenediamine (as a stabilizer) is charged into a 4-liter agitated glass vessel having a 1 meter glass column packed with glass Raschig rings and equipped with a water and a brine reflux condenser, interchangeable receiver, reflux control and vacuum control. A vacuum is produced and the vessel is heated by means of circulating hot water. At a vessel temperature of 60° C.
• a distillate starts passing over from the alcoholysis with a reflux ratio of 2:1.
• the vessel temperature rises to 70° C., and the overhead temperature is held between 33° and 36° C. by adjustment of the reflux ratio of 5:1.
• unreacted methyl methacrylate is withdrawn at a reflux ratio of 1:1 and a temperature of 50° C.
• the crude glycidyl methacrylate ester formed can be degassed down to a residual gas content of about 10%. After further degassing at 110° C.
• the ester formed in the vapor space and a vacuum of 30 mm Hg, can be distilled at 115° C. in the vapor space and 1 and 2 mm Hg. Yields over 80% are observed.
• the total time usually ranges from about 6 to 9 hours.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Epoxy Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

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Family Applications (1)

Country Status (6)

Cited By (2)

Citations (9)

• 1981
  • 1981-10-14 DE DE19813140764 patent/DE3140764A1/de active Granted
• 1982
  • 1982-09-07 FR FR8215158A patent/FR2514356B1/fr not_active Expired
  • 1982-09-10 IT IT8268081A patent/IT1156520B/it active
  • 1982-09-23 US US06/422,253 patent/US4418204A/en not_active Expired - Lifetime
  • 1982-10-08 JP JP57176441A patent/JPS5872576A/ja active Granted
  • 1982-10-13 GB GB08229292A patent/GB2107319B/en not_active Expired

Patent Citations (9)

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